Acid diamino-trjphenyl-methane dyestuffs



Patented Feb. 27, 1940 A 2,192,118 PATENT OFFICE son) nmmNo-TmrHENYL-METHANE DYE,-

STUF

Paul Herbert Wolff, deceased, late of Frankforton-the-Main-Hochst, Germany, by Richard Wenzel,

administrator,

Frankfort on the Q Main-Hochst, Germany, and Hans Moehrke and Gustav Schiifer, Frankfort-on-the-Main- Hochst, Germany, assignors to General Aniline & Film Corporation, a corporation of Dela- No'Drawing. Application March 21,1939, Serial No. 263,182. In Germany March 23, 1938 5 Claims. The present inventionr'elates to acid diaminotriphenyl-methane dyestuffs.

We have found that valuable acid diaminotriphenyl-methane dyestufis may beobtained by using, in processes known per se, aromatic amines containing, at the nitrogen, aliphatic radicals having 8 to 18 carbon atoms which may be branched or straight alkyl groups. There are obtained, for instance, dyestuffs of'the followin general formula:

wherein n means one of the numbers one. and

two, l

wherein X1 represents anialkyl group containing 8 to 18 carbon atoms,

X2 represents a member of the group consisting of hydrogen, alkyl and aralkyl of -the'benzene series,

X3 represents a member of the group consisting of aryl of the benzene series and alkyl containing 8 to 18 carbon atoms and Y represents a member of the group consisting of hydrogen and alkyl.

(1) Melting ketones with primary, secondary or tertiary amines, whereby each of the com-- ponents may contain one or more sulfo-groups and/or the dyestufi may be subjected to a subsequent sulfonation.

(2) Condensing benzhydroles' or benzhydrolesulfonic acids (obtainable, for instance, from tetrametyl-diamino-diphenyl-methane-' or from diethyl-dibenzyl diamino dipl'l'en'yl methanedisulfonic acid by oxidation to the hydrole), with substituted aromatic, isocyolic or heterocyclic bodies, for instance amines, phenols or sulfonic acids and oxidizing the leuco compounds obtained so as to form the dyestufi.

. sodium carbonate.

' '(3) Condensing aldehydes of the benzene or naphthalene series with primary, secondary or tertiary amines, whereby acid groups may be present in the components or may subsequently 'be introduced into the leuco compounds obtained and oxidizing the leuco compounds so as to form the dyestuff.

The following examples serve to illustrate the.

invention, but they are not intended to limit'itv thereto; the parts are by weight:

(1) 16 parts of alpha-naphthaldehyde and 86.2 parts of dodecylbenzyl-aniline-sulfonic acid of the formula:

(n)-dodecyl SOLE (obtainable from dodecylaniline by reaction with benzyl-chloride and sulfonation at ordinary temperature with six times its weight of fuming sulfuric acid containing 5% of sulfuric anhydride) are heated at 100 C. for hours with 120 parts of water and 5.5 parts of anhydrous The leuco dyestuff formed is precipitated with acid, dissolved in about 600 parts of water and the calculated amount of caustic sode solution and oxidized with lead dioxide in N-sulfuric acid so as to obtain the dyestuff. .It yields a very clear green tint and is distinguished by a good levelling power.

- (2) A mixture of 72.2 parts of dodecyl-benzaniline, 26.6 parts of benzaldehyde-ZA-disulfonic acid and 525 parts of sulfuric acid of 60% strength is heated at 100 C.-105 C. for hours. The leuco-sulfonic acid thus obtained is filtered with suction and transformed into its sodium salt by dissolving it in caustic soda solution. By

addition of 50 parts of oxalic acid, 20 parts of glacial acetic acid and 14.5 parts of sodium bichro- I mate to the solution at a temperature of 50 C.- C., a dyestufi is formed which may easily be isolated by salting out. It dyes wool greenblue tints and is distinguished by a very good levelling power.

(3) 26,6 parts of benzaldehyde-2,4-disulfonic acid and 47 parts of ethyl-octyl-aniline of the following formulaiare condensed in 250- parts of sulfuric acid of about 120 hours.

10% strength at 100 C. for about 100 hours. The leuco acid thus obtained is oxidized with sodium bichromate at C.- C., in the presence of sulfuric acid and oxalic acid, so as to obtain the dyestuff. By salting out, it separates in the form of its sodium salt; after drying, the dyestuff constitutes a blue powder which dyes wool and silk, in an acid bath, blue tints whichare distinguished by a good fastness to washing, fulling and sea-water. The dyestuff has the following probable formula:

octyl OH ethyl octyl ethyl SOsNa (5) 26.6 parts of benzaldehyde-2,4-disulfonic acid and 44 parts of mono-octyl-ortho-toluidine are condensed in 250 parts of sulfuric acid of 10% strength at a temperature of 100 C. for The leuco acid is separated and then oxidized, in known manner, by means of manganese dioxide, in the presence of dilute sulfuric acid. The dyestuff separates in the form of the sodium salt. It dyes wool, in an acid bath, reddish-blue tints which are distinguished by a good fastness to washing, fulling and sea-water.

The dyestuff corresponds with the following If, instead of octyl-ortho-toluidine, there are used 55 parts of dodecyl-ortho-toluidine or '72 parts of octodecyl-ortho-toluidine, dyestuffs having similar properties of fastness are obtained.

(6) 16.8 parts of benzaldehyde-ortho-sulfonic acid and 86.2 parts of dodecyl-benzyl aniline-sulfonic acid are condensedin 200 parts of water at 90 C.-100 C. for about 100 hours. The leuco acid is filtered with suction and oxidized with sodium bichromate in dilute acetic acid in the presence of oxalic'acid so as to form the dyestufi. After salting out. the dyestuff is obtained in the form of its sodium salt; it dyes'wool, in an acid bath, blue-green tints having a good fastness,

to wet processing.

If octyl-benzyl-m-toluidine-sulfonic acid or dodecyl-benzyl-m-toluidine-sulfonic' acid are used instead of dodecyl-benzyl-aniline-sulfonic acid, there are obtained dyestuffs hawing similar properties of fastness.

(7) A mixture of 35 parts of i-chlorobenzophenone-chloride 2-sulfoni c acid, 23.3 parts of ethyl-octyl-aniline, 150 parts of benzene and 16 parts-of zinc chloride is heated for 20' hours on the water-bath, while stirring under reflux. The

condensation product separates in the form of .a dark red resin; It is washed with benzene and dried.

49 parts of the condensation product thus obtained are heated at 100 C.- C., for about 4 hours, togetherwith 200 parts of para-phenetidine. The green dyestufi is isolated by stirring the whole several times with hydrochloric acid; it is then washed with water until neutral and dried.

The dyestuff obtained in. the form of the monosulfonic acid is dissolved in five times its weight of concentrated sulfuric acid and transformed into a disulfonic acidby heating the solution for 2-3 hours at 40 C. When precipitated in the usual manner, the dyestuff constitutes a green powder it dyes wool, in an acidbath, clear green tints which are distinguished by a good fastness to wet processing.

We claim: 1. The compounds of the general formula:

wherein 11. means one of the numbers one and 1 two,

wherein X1 represents an alkyl group containing 8 to 18 carbon atoms,

X2 represents a member of the group consisting of hydrogen, alkyl and aralkyl of the benzene; series, X3 represents a member of the group consisting of aryl of the benzene series and alkyl containing 8to 18 carbon atoms and Y represents a member of the group consisting of hydrogen and alkyl. p 2. The'compoundsof the general formula:

| S OaNa wherein X1 represents an alkyl group containing 8 to 18 carbon atoms,

X2 represents a member of the group consisting of hydrogen, alkyl and, aralkyl of the benzene series,

X3 represents a member of the group consisting v of aryl 'of thexbenzene series and alkyl containing 8 to 18 carbon atoms and Y represents a member of the group consisting of hydrogen and alkyl.

3. The compound of the formula:

being a blue powder whichdyes wool and silk, in an acid bath, blue tints which are distinguished by a. good fa'stness to washing, fulling and to sea-water.

4. The compound of the formula being a dyestuff which dyes W001 blue tints which are distinguished by a very good fastness to sea waiter. o

5. The compound. of the formula:

being a dyestufi which dyes wool, in an acid balth, reddish-blue tints which are distinguished by a. good fastness to washing, fulling and sea.-

Water. i v

RICHARD WENZEL,

' As administrator of Paul Herbert Wolfi, Deceased.

HANS MOEHRKE. GUSTAV scHAFER. 

